Catalytic hydroboration by an imido-hydrido complex of Mo(IV)

The imido-hydrido complex (ArN)Mo(H)(Cl)(PMe3)3 catalyses a variety of hydroboration reactions, including the first example of catalytic addition of HBCat to nitriles to form the bis(borylated) amines RCH2N(BCat)2. The latter species easily undergoes chemoselective coupling with aldehydes R0C(O)H to yield imines RCH2NQC(H)R

Catalytic hydroboration by an imido-hydrido complex of Mo(IV)

The imido-hydrido complex (ArN)Mo(H)(Cl)(PMe3)3 catalyses a variety of hydroboration reactions, including the first example of catalytic addition of HBCat to nitriles to form the bis(borylated) amines RCH2N(BCat)2. The latter species easily undergoes chemoselective coupling with aldehydes R0C(O)H to yield imines RCH2NQC(H)R

Multiple coupling of silanes with imido complexes of Mo

The bis(imido) complexes (tBuNv)2Mo(PMe3)(L) (L = PMe3, C2H4) react with up to three equivalents of silane PhSiH3 to give the imido-bridged disilyl silyl Mo(VI) complex (tBuN){μ-tBuN(SiHPh)2}Mo(H)(SiH2Ph)- (PMe3)2 (3) studied by NMR, IR and X-ray diffraction. NMR data supported by DFT calculations show that complex 3 is an unusual example of a silyl hydride of Mo(VI), without significant Si⋯H interaction. Mechanistic NMR studies revealed that silane addition proceeds in a stepwise manner via a series of Si–H⋯M agostic and silanimine complexes whose structures were further elucidated by DFT calculation

Multiple coupling of silanes with imido complexes of Mo

The bis(imido) complexes (tBuNv)2Mo(PMe3)(L) (L = PMe3, C2H4) react with up to three equivalents of silane PhSiH3 to give the imido-bridged disilyl silyl Mo(VI) complex (tBuN){μ-tBuN(SiHPh)2}Mo(H)(SiH2Ph)- (PMe3)2 (3) studied by NMR, IR and X-ray diffraction. NMR data supported by DFT calculations show that complex 3 is an unusual example of a silyl hydride of Mo(VI), without significant Si⋯H interaction. Mechanistic NMR studies revealed that silane addition proceeds in a stepwise manner via a series of Si–H⋯M agostic and silanimine complexes whose structures were further elucidated by DFT calculation

Western Beringia and beyond - three decades of German-Russian paleoenvironmental research on Siberian permafrost

With first joint fieldwork on Taymyr Peninsula during mid-1990s, a successful cooperation of German, Russian, and further international partners on permafrost and Quaternary palaeoenvironments in Siberia was started and resulted in extensive joint research for 3 decades. Studies of permafrost deposits and ground ice provided insights on past environmental and climatic changes, covering several hundreds of thousands of years into the past. They provide multi-proxy evidence for multiple glacial/interglacial cycles and different periods of past climate change or stability in Arctic land environments. Study objects were natural permafrost exposures along coastal sections, thaw slumps, and river banks, studied mostly during summers, complemented by permafrost cores from land, lake and sea ground drilled mostly in spring. Exposure geometry and stratigraphic horizon thickness have been surveyed using laser tachymetry, other measuring equipment, and drones. Based on multi-proxy analyses, mid- and late Quaternary periods were studied, resulting in >300 scientific papers. The approach includes geomorphic studies, various geochronological analyses, analysis of frozen sediments (for ice, carbon, nitrogen, and carbonate contents, grain-size parameters, magnetic susceptibility, heavy mineral compositions), ground ice (stable water isotopes, major ions) and of numerous fossil bioindicators, to reconstruct the Quaternary paleoenvironmental change. Oldest permafrost horizons were dated from the Batagay mega-thaw-slump (Yana Uplands) to about 650 ky with luminescence dating. Here and elsewhere, records of Eemian and Holocene interglacial periods, and environmental conditions associated with it were targeted. Many sites with late Pleistocene Yedoma Ice Complex have been explored. Lateglacial and Holocene warming induced enormous periglacial landscape changes by widespread permafrost degradation and substantial paleoecological changes. For vast Siberian areas where glacial records are not available, we aim on the establishment of permafrost as paleoclimatic archive, emphasizing peculiarities of permafrost age control and record resolution and stressing the great potential for understanding climate variability on glacial-interglacial timescales in Western Beringia

Development and implementation of blended courses for Russian language teachers in Russia and abroad

The growing popularity of massive open online courses (MOOC) stimulates teachers to appeal to the theory and practice of this philosophy. MOOCs are aimed at widespread involvement of students, improvement of their progress in studies, implementation of the principles of lifelong learning throughout life, support and development of their professional competence, etc. However, the mechanisms for implementing of the basic principles of MOOCs philosophy remain a subject of discussion. The article deals with theoretical approaches to solving a number of MOOCs problems connected with the use of a training video. The models for using a video content described in the article are given in the context of a blended Russian language learning project implemented at Kursk State University

Imido silyl complexes of molybdenum: synthesis, structure and unusual H2/silane exchange

Reaction of complex (ArN)Mo(H)(Cl)(PMe3)3 (1) with BPh3 and silane H3SiPh affords a new silyl complex (ArN)Mo(SiH2Ph)(Cl)(PMe3)2 (3) that catalyses facile H–H/Si–H exchange. EXSY experiments suggest that this exchange does not involve the classical pathways such as oxidative addition of hydrogen or silane to the complex or σ-bond metathesis. It is suggested that the exchange may occur in an FLP cage comprised by the complex and the silane.The accepted manuscript in pdf format is listed with the files at the bottom of this page. The presentation of the authors' names and (or) special characters in the title of the manuscript may differ slightly between what is listed on this page and what is listed in the pdf file of the accepted manuscript; that in the pdf file of the accepted manuscript is what was submitted by the author

Microbial tapestry of the Shulgan-Tash cave (Southern Ural, Russia): influences of environmental factors on the taxonomic composition of the cave biofilms

Abstract Background Cave biotopes are characterized by stable low temperatures, high humidity, and scarcity of organic substrates. Despite the harsh oligotrophic conditions, they are often inhabited by rich microbial communities. Abundant fouling with a wide range of morphology and coloration of colonies covers the walls of the Shulgan-Tash cave in the Southern Urals. This cave is also famous for the unique Paleolithic painting discovered in the middle of the last century. We aimed to investigate the diversity, distribution, and potential impact of these biofilms on the cave’s Paleolithic paintings, while exploring how environmental factors influence the microbial communities within the cave. Results The cave’s biofilm morphotypes were categorized into three types based on the ultrastructural similarities. Molecular taxonomic analysis identified two main clusters of microbial communities, with Actinobacteria dominating in most of them and a unique “CaveCurd” community with Gammaproteobacteria prevalent in the deepest cave sections. The species composition of these biofilms reflects changes in environmental conditions, such as substrate composition, temperature, humidity, ventilation, and CO2 content. Additionally, it was observed that cave biofilms contribute to biocorrosion on cave wall surfaces. Conclusions The Shulgan-Tash cave presents an intriguing example of a stable extreme ecosystem with diverse microbiota. However, the intense dissolution and deposition of carbonates caused by Actinobacteria pose a potential threat to the preservation of the cave’s ancient rock paintings